CN107604231B - A kind of high pressure resistant high-temperature rigid alloy and preparation method thereof - Google Patents
A kind of high pressure resistant high-temperature rigid alloy and preparation method thereof Download PDFInfo
- Publication number
- CN107604231B CN107604231B CN201710821976.9A CN201710821976A CN107604231B CN 107604231 B CN107604231 B CN 107604231B CN 201710821976 A CN201710821976 A CN 201710821976A CN 107604231 B CN107604231 B CN 107604231B
- Authority
- CN
- China
- Prior art keywords
- parts
- carbide
- temperature
- partial size
- pressure resistant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention belongs to powder metallurgical technologies more particularly to a kind of high pressure resistant high-temperature rigid alloy and preparation method thereof.High pressure resistant high-temperature rigid alloy provided by the invention, including the following raw material and its mass fraction: 0.1-1.0 parts of cobalt, 0.1-0.3 parts of rhodium, 0.5-1 parts of carbonyl nickel powder, 0.1-1.0 parts of vanadium carbide, 10-20 parts of tantalum carbide, 0.6-1.0 parts of niobium carbide, 2.0-4.0 parts of titanium carbide, 0.3-0.5 parts of hafnium carbide, 0.1-0.5 parts of aluminium nitride and 75-90 parts of tungsten carbide.In high pressure resistant high-temperature rigid alloy provided by the invention, tungsten carbide partial size is smaller and is evenly distributed, mean grain size reach 0.10-0.25 μm, meanwhile, high pressure resistant high-temperature rigid alloy rigidity provided by the invention is up to HRA96.5, and bending strength is up to 3400N/mm2, compression strength is up to 5200MPa, with good high pressure resistant, high temperature resistance.
Description
Technical field
The invention belongs to powder metallurgical technology more particularly to a kind of high pressure resistant high-temperature rigid alloy and its preparation sides
Method.
Background technique
Hard alloy is hard compounds and binding metal one kind made of powder metallurgical technique of refractory metal
Alloy material has a series of excellent performances such as hardness is high, wear-resisting, intensity and toughness are preferable, heat-resisting, corrosion-resistant, is known as " work
Industry tooth " is widely used in the fields such as cutter material, machining, aerospace, high pressure-temperature test.It is universal on domestic market
The Cemented Carbide Hardness of application up to HRA86-93, even if 500 DEG C at a temperature of be held essentially constant, still at 1000 DEG C
Keep high rigidity.
In the high pressure-temperature test, due to can reach in test cavity body 10-20GPa or more pressure and 2000 DEG C or more
Temperature, subjects superelevation compression, tensile stress and high temperature etc., and lower work in a supercritical state leads to common hard alloy
Thermohardening reduces under such high temperature and high pressure environment, is easy to produce deformation, and therefore, current domestic hard alloy on the market is only
It can be used for primary high-potting, experimentation cost to be high, and working efficiency is low, and greatly wastes rare metal resources.
Chinese patent application CN106282723A discloses a kind of hard alloy and preparation method thereof that high temperature hardness is strong, institute
Stating metal alloy includes following raw material: 36-52 parts of titanium nitride, 25-34 parts of lithium nitride, 13-18 parts of two chromium boride, tantalum nitride 8-15
Part, 10-14 parts of niobium carbide, binder are cobalt 6-10 parts；Preparation method includes: that each powder raw material investment ball mill is carried out ball
Mill, rotational speed of ball-mill 300-360r/min, Ball-milling Time 24-72h；Mixture sieving, dry, granulation after ball milling is obtained hard
The forming agent that dosage is hard alloy material weight 5-8%, the forming agent are added in the granulating working procedure for matter alloy mixture
Any one at least in polyvinyl alcohol, rubber and paraffin；By the repressed molding of mixture, pressing pressure 210-
270MPa；Carrying out degreasing process, skimming temp is 210-320 DEG C, 1-6 DEG C/min of heating rate, heat preservation 15 minutes or more,
The semi-finished product of compression moulding are sintered, using inert gas sintering or vacuum-sintering, 1450-1520 DEG C of sintering temperature, heating is fast
Rate is 3-6 DEG C/min, every heating primary heat preservation 4-8 minutes.The hard alloy high temperature hardness of the invention is high, has both and reaches industry
The wearability and tough of standard.
Chinese patent application CN106191606A discloses a kind of high temperature cemented carbide, and the hard alloy presses quality hundred
Divide than its component are as follows: Co 3-6%, Ni 8-12%, TaC and Cr2C3For 1-3%, WC 79-88%.The hard of the invention closes
1900-2450N/mm under golden bending strength room temperature2, hard alloy mechanical property under working environment is improved, effectively inhibits to close
Plastic deformation under golden high temperature.
The preferable hard alloy of high pressure resistant high-temperature behavior is made in above two scheme, but in scheme metallic cobalt content compared with
Height, cobalt is a kind of expensive and has the metal material centainly influenced on human health, therefore, from human health, reduces cost
Consider with high pressure resistant high-temperature behavior of hard alloy etc. is improved, still lack in the prior art one kind can reduce experimentation cost,
It improves working efficiency, save a kind of high pressure resistant high-temperature rigid alloy of rare metal resources for country.
Summary of the invention
In order to solve the technical problems existing in the prior art, the purpose of the present invention is to provide a kind of high pressure resistant high temperature is hard
Matter alloy and preparation method thereof.High pressure resistant high-temperature rigid alloy provided by the invention improves hard alloy by refinement crystal grain
Hardness, bending strength and compression strength, make the hardness of hard alloy up to HRA96.5, and bending strength reaches 3400N/mm2, pressure resistance
Degree reach 5200MPa, and then make hard alloy have good high pressure resistant, high temperature resistance, 10-20GPa or more pressure and
Still reusable 3 times or more under 2000 DEG C or more of state of temperature, prolong the service life, reduces work consume, improve work
Efficiency, and rare metal resources are saved for country.
Technical scheme is as follows:
A kind of high pressure resistant high-temperature rigid alloy, including the following raw material and its mass fraction: 0.1-1.0 parts of cobalt, rhodium 0.1-0.3
Part, 0.5-1.0 parts of carbonyl nickel powder, 0.1-1.0 parts of vanadium carbide, 10-20 parts of tantalum carbide, 0.6-1.0 parts of niobium carbide, titanium carbide 2.0-
4.0 parts, 0.3-0.5 parts of hafnium carbide, 0.1-0.5 parts of aluminium nitride and 75-90 parts of tungsten carbide.
Preferably, the high pressure resistant high-temperature rigid alloy, including the following raw material and its mass fraction: 0.3-0.7 parts of cobalt, rhodium
0.2 part, 0.6-0.9 parts of carbonyl nickel powder, 0.3-0.8 parts of vanadium carbide, 12-18 parts of tantalum carbide, 0.7-0.8 parts of niobium carbide, titanium carbide 3
Part, 0.4 part of hafnium carbide, 0.2-0.4 parts of aluminium nitride and 80-85 parts of tungsten carbide.
More preferred, the high pressure resistant high-temperature rigid alloy, including the following raw material and its mass fraction: 0.4 part of cobalt, rhodium
0.2 part, 0.7 part of carbonyl nickel powder, 0.5 part of vanadium carbide, 14 parts of tantalum carbide, 0.7 part of niobium carbide, 3 parts of titanium carbide, 0.4 part of hafnium carbide,
0.3 part and 82 parts of tungsten carbide of aluminium nitride.
Preferably, the tungsten carbide partial size is 0.25-0.35 μm, and the cobalt button diameter is 0.3-0.6 μm, and the rhodium partial size is
0.4-0.6 μm, the carbonyl nickel powder partial size is 0.45-0.65 μm, and the vanadium carbide partial size is 0.15-0.6 μm, the tantalum carbide
Partial size is 0.4-0.8 μm, and the niobium carbide partial size is 0.4-1 μm, and the titanium carbide partial size is 0.2-0.8 μm, the hafnium carbide
Partial size is 0.1-0.3 μm, the aluminium nitride partial size is 0.3-0.6 μm.
In addition, including the following steps: the present invention also provides a kind of preparation method of high pressure resistant high-temperature rigid alloy
S1: taking all raw materials by definite quality number, and addition ball-milling medium, which is placed in ball mill, after mixing carries out
Ball milling, liquid-solid ratio 475-550mL/kg, ratio of grinding media to material 5.5-6.5: 1, drum's speed of rotation are controlled in 60-135r/min, ball milling
Time is 70-110h, obtains wet mixture A；
S2: wet mixture A obtained by step S1 is fitted into drier dry 1.5-2h, carries out ball-milling medium recycling, then
Circulating cooling is carried out with chilled water, sieves to obtain mixture B, then carries out above-mentioned mixture B in the state of sealing to mix wax, system
Mixture C is made in grain；
S3: by mixture C isostatic pressing obtained by step S2, pressure is controlled in 150-280MPa, and green compact is made；
S4: high pressure resistant high-temperature rigid alloy is made using the positive carbon high-temp sintering process of low pressure in green compact made from step S3.
Preferably, ball-milling medium includes following ingredient and weight percent: absolute alcohol 97.5- in the step S1
99.2Wt%, oleic acid 0.8-2.5Wt%.
More preferred, ball-milling medium includes following ingredient and weight percent: absolute alcohol in the step S1
98.7Wt%, oleic acid 1.3Wt%.
Preferably, liquid-solid ratio is 520mL/kg in the step S1, and ratio of grinding media to material 6: 1, drum's speed of rotation control is in 105r/
Min, Ball-milling Time 95h.
Preferably, wet mixture is fitted into drier dry 2h in the step S2.
Preferably, pressure is controlled in 260MPa in the step S3.
Preferably, the positive carbon high-temp sintering process of the step S4 mesolow includes the following steps:
1) it charges, vacuumizes；
2) it is warming up to 350-600 DEG C of dewaxing, keeps the temperature 1-3h；
3) it is warming up to 1100-1350 DEG C, keeps the temperature 0.5-2h；
4) 1450-1550 DEG C of low temperature carburization 0.5-2h；
5) it is warming up to 1600 DEG C of final sintering temperature, applying argon gas pressurization, pressure is controlled in 5-10MPa, heat-insulating pressurizing 1-2h；
6) decompression cooling, discharging.
More preferred, the positive carbon high-temp sintering process of step S4 mesolow includes the following steps:
1) it charges, vacuumizes；
2) 600 DEG C of dewaxings are warming up to, 3h is kept the temperature；
3) 1200 DEG C are warming up to, 1h is kept the temperature；
4) 1550 DEG C of low temperature carburization 2h；
5) it is warming up to 1600 DEG C of final sintering temperature, applying argon gas pressurization, pressure is controlled in 8MPa, heat-insulating pressurizing 1.5h；
6) decompression cooling, discharging.
In the present invention, all raw materials are the smaller superfine powder between 0.1-1 μm of partial size, and sintering is made to be easier densification.This
The tungsten carbide that invention is 0.25-0.35 μm using partial size is as raw material powder, and the cobalt that partial size is 0.3-0.6 μm is as adhesive；Add
Add vanadium carbide to reduce Cemented Carbide Properties to the sensibility of sintering temperature and time, makes the burning of hard alloy magnetic force and hardness qualification
The range of junction temperature and time increase；Addition tantalum carbide, niobium carbide, titanium carbide composition composite grain grow up inhibitor, inhibit
Tungsten carbide crystal grain is grown up, and WC grain degree in hard alloy is made to enhance the hardness of hard alloy less than 0.25 μm；Add a small amount of carbonyl
Nickel powder makes Powder during Sintering Process diafiltration uniformly, increases the toughness of hard alloy；In addition to this, the present invention adds hafnium carbide and nitridation
Aluminium originally means enhancing Cemented Carbide Hardness and bending strength, however has been surprisingly found that during the test, adds hafnium carbide and nitridation
Aluminium can enhance hard alloy consistency, and then extend hard alloy service life.
There are two types of crystal structures for metal Co tool: the α-Co of hexagonal structure and face-centred cubic β-Co, the α-Co of hexagonal structure
With excellent compatibility of deformation, and β-Co has excellent intensity, and part at a high temperature of 417 DEG C or more α-Co turns to β-Co
Become.The big more options addition metal zirconium of the prior art or rare earth element enhancing Co bond phase, inhibit α-Co to change to β-Co with this, from
And the hard alloy of high-flexural strength is obtained, however this way reduces the hardness of hard alloy to a certain extent.This hair
Bright inventor α-Co and β-Co content from balance Co Binder Phase have done a large number of experiments, and discovery is added in hard alloy
The content of α-Co and β-Co in Co Binder Phase under high temperature, mechanism is adjusted in a small amount of metal rhodium are as follows: metal rhodium hardness is high, intensity
Greatly, the cenotype being precipitated after a small amount of rhodium in alloy based on rhodium is added in hard alloy, this mutually exists in the form of independent phase, seldom
It is dissolved in Binder Phase, invigoration effect is played to Binder Phase, α-Co is inhibited to change to β-Co to a certain extent, and rhodium is vertical for the center of area
Square structure provides stable structural environment in hard alloy for face-centred cubic β-Co, also ensures to a certain extent hard
The content of β-Co in matter alloy.The present invention balances α-Co and β-Co content in hard alloy by adding metal rhodium, and then makes
The high pressure resistant high-temperature rigid alloy of high rigidity, high-flexural strength and compression strength must be had both.
The present invention is sintered under the conditions of 1600 DEG C of final temperature and pressure 5-10MPa using the positive carbon high-temp sintering process of low pressure
Hard alloy, the application of the positive carbon high-temp sintering process of low pressure in the present invention have 3 effects: (1) flat using a small amount of organic carbon source
The carbon content for the final product that weighs compensates in production process hard metal article blank surface oxide in high-temperature sintering process
It is chemically reacted with carbon, generates CO or CO2Caused by carbon it is insufficient, help to improve the mechanical property of hard alloy；(2) low
A possibility that sintering of positive pressure carbon high-temp applies the pressure of 5-10Pa, this makes crystallite dimension grow up greatly reduces, and greatlys improve
The consistency of sintered hard alloy；(3) the positive carbon high-temp sintering of low pressure is conducive to the combination between hard phase and binder, so that
Interface bond strength, hardness significantly improve.
Compared with prior art, high pressure resistant high-temperature rigid alloy provided by the invention has the advantage that
(1) high pressure resistant high-temperature rigid alloy provided by the invention, hardness is up to HRA96.5, and bending strength is up to 3400N/
mm2, compression strength is up to 5200MPa, with good high temperature resistant, high voltage performance；
(2) high pressure resistant high-temperature rigid alloy provided by the invention, can effectively inhibit hard alloy under high pressure-temperature
Plastic deformation, still be able to reuse 3 times under the state of temperature of the pressure of 10-20GPa or more and 2000 DEG C or more or more；
(3) high pressure resistant high-temperature rigid alloy provided by the invention is applied in high pressure-temperature test, can be effectively reduced examination
Cost is tested, improves working efficiency, while saving rare metal resources for country.
Specific embodiment
The present invention is further described below by way of specific embodiment, but the present invention is not limited only to following embodiment.
Embodiment 1, high pressure resistant high-temperature rigid alloy
The high pressure resistant high-temperature rigid alloy is made of following component and its mass fraction: the cobalt 0.1 that partial size is 0.3 μm
Part, 0.1 part of the rhodium that partial size is 0.4 μm, 1.0 parts of the carbonyl nickel powder that partial size is 0.45 μm, the vanadium carbide 1.0 that partial size is 0.15 μm
Part, 10 parts of the tantalum carbide that partial size is 0.4 μm, 0.6 part of the niobium carbide that partial size is 0.4 μm, 2.0 parts of the titanium carbide that partial size is 0.2 μm,
0.3 part of the hafnium carbide that partial size is 0.1 μm, 0.1 part of the aluminium nitride that partial size is 0.3 μm, 75 parts of tungsten carbide that partial size is 0.25 μm.
Preparation method:
S1: taking all raw materials by definite quality number, and addition ball-milling medium, which is placed in ball mill, after mixing carries out
Ball milling, the ball-milling medium are made of the absolute alcohol of 97.8Wt% and the oleic acid of 2.2Wt%, liquid-solid ratio 500mL/kg, ball
Than being 5.5: 1, drum's speed of rotation is controlled in 135r/min, Ball-milling Time 70h material, obtains wet mixture A；
S2: wet mixture A obtained by step S1 is fitted into drier dry 1.5h, ball-milling medium recycling is carried out, then uses
Chilled water carries out circulating cooling, sieves to obtain mixture B, then carries out above-mentioned mixture B in the state of sealing to mix wax, system
Mixture C is made in grain；
S3: by mixture C isostatic pressing obtained by step S2, pressure is controlled in 220MPa, and green compact is made；
S4: green compact made from step S3 is sintered in low-pressure sintering furnace with the positive carbon high-temp sintering process of low pressure: 1) charging, takes out
Vacuum；2) 500 DEG C of dewaxings are warming up to, 1h is kept the temperature；3) 1300 DEG C are warming up to, 1h is kept the temperature；4) 1550 DEG C of low temperature carburization 2h；5) it heats up
To 1600 DEG C of final sintering temperature, applying argon gas pressurization, pressure is controlled in 7MPa, heat-insulating pressurizing 2h；6) decompression cooling, discharging, i.e.,
?.
Embodiment 2, high pressure resistant high-temperature rigid alloy
The high pressure resistant high-temperature rigid alloy is made of following component and its mass fraction: the cobalt 1.0 that partial size is 0.6 μm
Part, 0.3 part of the rhodium that partial size is 0.6 μm, 0.5 part of the carbonyl nickel powder that partial size is 0.65 μm, 0.1 part of the vanadium carbide that partial size is 0.6 μm,
20 parts of the tantalum carbide that partial size is 0.8 μm, 1.0 parts of the niobium carbide that partial size is 1 μm, 4.0 parts of the titanium carbide that partial size is 0.8 μm, partial size
For 0.3 μm of 0.5 part of hafnium carbide, 0.5 part of the aluminium nitride that partial size is 0.6 μm, 90 parts of tungsten carbide that partial size is 0.35 μm.
Preparation method:
S1: taking all raw materials by definite quality number, and addition ball-milling medium, which is placed in ball mill, after mixing carries out
Ball milling, the ball-milling medium are made of the absolute alcohol of 99.2Wt% and the oleic acid of 0.8Wt%, liquid-solid ratio 550mL/kg, ball
Than being 6.2: 1, drum's speed of rotation is controlled in 60r/min, Ball-milling Time 110h material, obtains wet mixture A；
S2: wet mixture A obtained by step S1 is fitted into drier dry 1.8h, ball-milling medium recycling is carried out, then uses
Chilled water carries out circulating cooling, sieves to obtain mixture B, then carries out above-mentioned mixture B in the state of sealing to mix wax, system
Mixture C is made in grain；
S3: by mixture C isostatic pressing obtained by step S2, pressure is controlled in 280MPa, and green compact is made；
S4: green compact made from step S3 is sintered in low-pressure sintering furnace with the positive carbon high-temp sintering process of low pressure: 1) charging, takes out
Vacuum；2) 350 DEG C of dewaxings are warming up to, 1.5h is kept the temperature；3) 1350 DEG C are warming up to, 1h is kept the temperature；4) 1550 DEG C of low temperature carburization 2h；5) it rises
Temperature to 1600 DEG C of final sintering temperature, applying argon gas pressurization, pressure is controlled in 5MPa, heat-insulating pressurizing 2h；6) decompression cooling, discharging,
To obtain the final product.
Embodiment 3, high pressure resistant high-temperature rigid alloy
The high pressure resistant high-temperature rigid alloy is made of following component and its mass fraction: the cobalt 0.4 that partial size is 0.4 μm
Part, 0.2 part of the rhodium that partial size is 0.5 μm, 0.7 part of the carbonyl nickel powder that partial size is 0.5 μm, 0.5 part of the vanadium carbide that partial size is 0.3 μm,
14 parts of the tantalum carbide that partial size is 0.5 μm, 0.7 part of the niobium carbide that partial size is 0.6 μm, 3 parts of titanium carbide that partial size is 0.4 μm, partial size
For 0.2 μm of 0.4 part of hafnium carbide, 0.3 part of the aluminium nitride that partial size is 0.4 μm, 82 parts of tungsten carbide that partial size is 0.3 μm.
Preparation method:
S1: taking all raw materials by definite quality number, and addition ball-milling medium, which is placed in ball mill, after mixing carries out
Ball milling, the ball-milling medium are made of the absolute alcohol of 98.7Wt% and the oleic acid of 1.3Wt%, liquid-solid ratio 520mL/kg, ball
Than being 6: 1, drum's speed of rotation is controlled in 105r/min, Ball-milling Time 95h material, obtains wet mixture A；
S2: wet mixture A obtained by step S1 is fitted into drier dry 2h, ball-milling medium recycling is carried out, then with cold
Freeze water and carry out circulating cooling, sieve to obtain mixture B, then by above-mentioned mixture B carry out mixing in the state of sealing wax, granulation,
Mixture C is made；
S3: by mixture C isostatic pressing obtained by step S2, pressure is controlled in 260MPa, and green compact is made；
S4: green compact made from step S3 is sintered in low-pressure sintering furnace with the positive carbon high-temp sintering process of low pressure: 1) charging, takes out
Vacuum；2) 600 DEG C of dewaxings are warming up to, 3h is kept the temperature；3) 1200 DEG C are warming up to, 1h is kept the temperature；4) 1550 DEG C of low temperature carburization 2h；5) it heats up
To 1600 DEG C of final sintering temperature, applying argon gas pressurization, pressure is controlled in 8MPa, heat-insulating pressurizing 1.5h；6) decompression cooling, discharging,
To obtain the final product.
Embodiment 4, high pressure resistant high-temperature rigid alloy
The high pressure resistant high-temperature rigid alloy is made of following component and its mass fraction: the cobalt 0.7 that partial size is 0.5 μm
Part, 0.2 part of the rhodium that partial size is 0.5 μm, 0.6 part of the carbonyl nickel powder that partial size is 0.6 μm, 0.3 part of the vanadium carbide that partial size is 0.5 μm,
18 parts of the tantalum carbide that partial size is 0.7 μm, 0.8 part of the niobium carbide that partial size is 0.8 μm, 3 parts of titanium carbide that partial size is 0.6 μm, partial size
For 0.2 μm of 0.4 part of hafnium carbide, 0.4 part of aluminium nitride that partial size is 0.5 μm, partial size is 85 parts of tungsten carbide of 0.32 μm.
Preparation method:
S1: taking all raw materials by definite quality number, and addition ball-milling medium, which is placed in ball mill, after mixing carries out
Ball milling, the ball-milling medium are made of the absolute alcohol of 97.5Wt% and the oleic acid of 2.5Wt%, liquid-solid ratio 475mL/kg, ball
Than being 6.5: 1, drum's speed of rotation is controlled in 120r/min, Ball-milling Time 80h material, obtains wet mixture A；
S2: wet mixture A obtained by step S1 is fitted into drier dry 2h, ball-milling medium recycling is carried out, then with cold
Freeze water and carry out circulating cooling, sieve to obtain mixture B, then by above-mentioned mixture B carry out mixing in the state of sealing wax, granulation,
Mixture C is made；
S3: by mixture C isostatic pressing obtained by step S2, pressure is controlled in 150MPa, and green compact is made；
S4: green compact made from step S3 is sintered in low-pressure sintering furnace with the positive carbon high-temp sintering process of low pressure: 1) charging, takes out
Vacuum；2) 600 DEG C of dewaxings are warming up to, 3h is kept the temperature；3) 1350 DEG C are warming up to, 2h is kept the temperature；4) 1550 DEG C of low temperature carburization 2h；5) it heats up
To 1600 DEG C of final sintering temperature, applying argon gas pressurization, pressure is controlled in 10MPa, heat-insulating pressurizing 2h；6) decompression cooling, discharging, i.e.,
?.
Embodiment 5, high pressure resistant high-temperature rigid alloy
The high pressure resistant high-temperature rigid alloy, is made of the raw material of following mass fraction: the cobalt 0.3 that partial size is 0.45 μm
Part, 0.2 part of the rhodium that partial size is 0.5 μm, 0.9 part of the carbonyl nickel powder that partial size is 0.55 μm, the vanadium carbide 0.8 that partial size is 0.38 μm
Part, 12 parts of the tantalum carbide that partial size is 0.6 μm, 0.7 part of the niobium carbide that partial size is 0.7 μm, 3 parts of titanium carbide that partial size is 0.5 μm, grain
0.4 part of the hafnium carbide that diameter is 0.2 μm, 0.2 part of the aluminium nitride that partial size is 0.5 μm, 80 parts of tungsten carbide that partial size is 0.27 μm.
Preparation method:
S1: taking all raw materials by definite quality number, and addition ball-milling medium, which is placed in ball mill, after mixing carries out
Ball milling, the ball-milling medium are made of the absolute alcohol of 98.7Wt% and the oleic acid of 1.3Wt%, liquid-solid ratio 520mL/kg, ball
Than being 6: 1, drum's speed of rotation is controlled in 105r/min, Ball-milling Time 100h material, obtains wet mixture A；
S2: wet mixture A obtained by step S1 is fitted into drier dry 2h, ball-milling medium recycling is carried out, then with cold
Freeze water and carry out circulating cooling, sieve to obtain mixture B, then by above-mentioned mixture B carry out mixing in the state of sealing wax, granulation,
Mixture C is made；
S3: by mixture C isostatic pressing obtained by step S2, pressure is controlled in 260MPa, and green compact is made；
S4: green compact made from step S3 is sintered in low-pressure sintering furnace with the positive carbon high-temp sintering process of low pressure: 1) charging, takes out
Vacuum；2) 550 DEG C of dewaxings are warming up to, 2.5h is kept the temperature；3) 1100 DEG C are warming up to, 0.5h is kept the temperature；4) 1450 DEG C of low temperature carburization 0.5h；
5) it is warming up to 1600 DEG C of final sintering temperature, applying argon gas pressurization, pressure is controlled in 6MPa, heat-insulating pressurizing 1h；6) decompression cooling, is unloaded
Material to get.
Comparative example 1, high pressure resistant high-temperature rigid alloy
The high pressure resistant high-temperature rigid alloy is made of following component and its mass fraction: the cobalt 0.4 that partial size is 0.4 μm
Part, 0.2 part of the zirconium that partial size is 0.5 μm, 0.7 part of the carbonyl nickel powder that partial size is 0.5 μm, 0.5 part of vanadium carbide that partial size is 0.3 μm,
14 parts of the tantalum carbide that partial size is 0.5 μm, 0.7 part of the niobium carbide that partial size is 0.6 μm, 3 parts of titanium carbide that partial size is 0.4 μm, partial size
For 0.2 μm of 0.4 part of hafnium carbide, 0.3 part of the aluminium nitride that partial size is 0.4 μm, 82 parts of tungsten carbide that partial size is 0.3 μm.
Preparation method is similar to Example 3.
Difference with embodiment 3 is that being changed to metal rhodium in raw material in the prior art, there is enhancing Co bonding mutually to make
Metal zirconium.
Comparative example 2, high pressure resistant high-temperature rigid alloy
The component and its mass fraction of the high pressure resistant high-temperature rigid alloy are the same as embodiment 3.
The high pressure resistant high-temperature rigid alloy each component partial size is the same as embodiment 3.
Preparation method:
S1: taking all raw materials by definite quality number, and addition ball-milling medium, which is placed in ball mill, after mixing carries out
Ball milling, the grinding media are made of the absolute alcohol of 98.7Wt% and the oleic acid of 1.3Wt%, liquid-solid ratio 520mL/kg, ball material
Than being 6: 1, drum's speed of rotation is controlled in 105r/min, Ball-milling Time 95h, obtains wet mixture A；
S2: wet mixture A obtained by step S1 is fitted into drier dry 2h, ball-milling medium recycling is carried out, then with cold
Freeze water and carry out circulating cooling, sieve to obtain mixture B, then by above-mentioned mixture B carry out mixing in the state of sealing wax, granulation,
Mixture C is made；
S3: by mixture C isostatic pressing obtained by step S2, pressure is controlled in 260MPa, and green compact is made；
S4: green compact made from step S3 is sintered, and sintering method is real with reference to Chinese patent application CN106077668A
It applies example 1: green compact obtained in S3 is put into hot isostatic press high-pressure bottle, apply 1500 DEG C -1600 DEG C, pressure exists
130MPa-140MPa, be sintered 23h after, be cooled to room temperature to get.
The performance test of test example 1, high pressure resistant high-temperature rigid alloy
1, test material: high pressure resistant high-temperature rigid alloy made from embodiment 1-5, comparative example 1 and comparative example 2.
2, test method:
Using Rockwell apparatus to high pressure resistant high-temperature rigid alloy made from embodiment 1-5, comparative example 1 and comparative example 2 into
Row hardness determination.
High pressure resistant high-temperature rigid made from embodiment 1-5, comparative example 1 and comparative example 2 is closed using universal testing machine
Gold carries out bending strength detection.
Using pressure testing machine to high pressure resistant high-temperature rigid alloy made from embodiment 1-5, comparative example 1 and comparative example 2 into
The detection of row compression strength.
Using metallographic microscope to high pressure resistant high-temperature rigid alloy made from embodiment 1-5, comparative example 1 and comparative example 2 into
The detection of row mean grain size.
3, test result:
Every testing result is as shown in table 1:
The performance test results of each high pressure resistant high-temperature rigid alloy in 1 embodiment of table, comparative example
As shown in Table 1, the tungsten carbide mean grain size of the high pressure resistant high-temperature rigid alloy of the present invention is small, hardness, bending strength
Be significantly better than hard alloy made from comparative example with compression strength, it is especially best with the performance of embodiment 3, hardness HRA up to 96.5,
Bending strength reaches 3392N/mm2, compression strength reach 5196MPa, 0.14 μm of tungsten carbide mean grain size, have good resistance to height
Temperature, high voltage performance can effectively inhibit hard alloy in the state of temperature of the pressure of 10-20GPa or more and 2000 DEG C or more
Under plastic deformation, make hard alloy still reusable 3 times or more under high pressure-temperature, prolong the service life, reduce work
Consume improves working efficiency, and saves rare metal resources for country.
Basic principles and main features and advantages of the present invention of the invention, the technology of the industry has been shown and described above
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these variation and
Improvement is both fallen within the scope of claimed invention, and the claimed scope of the invention is by appended claims and its equivalent
It defines.
Claims (6)
1. a kind of high pressure resistant high-temperature rigid alloy, which is characterized in that including the following raw material and its mass fraction: 0.1-1.0 parts of cobalt,
0.1-0.3 parts of rhodium, 0.5-1.0 parts of carbonyl nickel powder, 0.1-1.0 parts of vanadium carbide, 10-20 parts of tantalum carbide, 0.6-1.0 parts of niobium carbide,
2.0-4.0 parts of titanium carbide, 0.3-0.5 parts of hafnium carbide, 0.1-0.5 parts of aluminium nitride and 75-90 parts of tungsten carbide；The tungsten carbide partial size
It is 0.25-0.35 μm, the cobalt button diameter is 0.3-0.6 μm, and the rhodium partial size is 0.4-0.6 μm, and the carbonyl nickel powder partial size is
0.45-0.65 μm, the vanadium carbide partial size is 0.15-0.6 μm, and the tantalum carbide partial size is 0.4-0.8 μm, the niobium carbide grain
Diameter is 0.4-1 μm, and the titanium carbide partial size is 0.2-0.8 μm, and the hafnium carbide partial size is 0.1-0.3 μm, the nitridation aluminum shot
Diameter is 0.3-0.6 μm.
2. high pressure resistant high-temperature rigid alloy as described in claim 1, which is characterized in that including the following raw material and its mass parts
Number: 0.3-0.7 parts of cobalt, 0.2 part of rhodium, 0.6-0.9 parts of carbonyl nickel powder, 0.3-0.8 parts of vanadium carbide, 12-18 parts of tantalum carbide, niobium carbide
0.7-0.8 parts, 3 parts of titanium carbide, 0.4 part of hafnium carbide, 0.2-0.4 parts of aluminium nitride and 80-85 parts of tungsten carbide.
3. high pressure resistant high-temperature rigid alloy as claimed in claim 2, which is characterized in that including the following raw material and its mass parts
Number: 0.4 part of cobalt, 0.2 part of rhodium, 0.7 part of carbonyl nickel powder, 0.5 part of vanadium carbide, 14 parts of tantalum carbide, 0.7 part of niobium carbide, titanium carbide 3
Part, 0.4 part of hafnium carbide, 0.3 part of aluminium nitride and 82 parts of tungsten carbide.
4. a kind of preparation method of high pressure resistant high-temperature rigid alloy as described in any one of claims 1-3, which is characterized in that packet
Include following steps:
S1: taking all raw materials by definite quality number, and addition ball-milling medium, which is placed in ball mill, after mixing carries out ball milling,
Liquid-solid ratio is 475-550mL/kg, and ratio of grinding media to material 5.5-6.5:1, in 60-135r/min, Ball-milling Time is for drum's speed of rotation control
70-110h obtains wet mixture A；
S2: wet mixture A obtained by step S1 is fitted into drier dry 1.5-2h, ball-milling medium recycling is carried out, then with cold
Freeze water and carry out circulating cooling, sieve to obtain mixture B, then by above-mentioned mixture B carry out mixing in the state of sealing wax, granulation,
Mixture C is made；
S3: by mixture C isostatic pressing obtained by step S2, pressure is controlled in 150-280MPa, and green compact is made；
S4: high pressure resistant high-temperature rigid alloy is made using the positive carbon high-temp sintering process of low pressure in green compact made from step S3.
5. the preparation method of high pressure resistant high-temperature rigid alloy as claimed in claim 4, which is characterized in that ball in the step S1
Grinding media includes following ingredient and weight percent: absolute alcohol 97.5-99.2Wt%, oleic acid 0.8-2.5Wt%.
6. the preparation method of high pressure resistant high-temperature rigid alloy as claimed in claim 4, which is characterized in that low in the step S4
Positive pressure carbon high-temp sintering process includes the following steps:
1) it charges, vacuumizes；
2) it is warming up to 350-600 DEG C of dewaxing, keeps the temperature 1-3h；
3) it is warming up to 1100-1350 DEG C, keeps the temperature 0.5-2h；
4) 1450-1550 DEG C of low temperature carburization 0.5-2h；
5) it is warming up to 1600 DEG C of final sintering temperature, applying argon gas pressurization, pressure is controlled in 5-10MPa, heat-insulating pressurizing 1-2h；
6) decompression cooling, discharging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710821976.9A CN107604231B (en) | 2017-09-12 | 2017-09-12 | A kind of high pressure resistant high-temperature rigid alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710821976.9A CN107604231B (en) | 2017-09-12 | 2017-09-12 | A kind of high pressure resistant high-temperature rigid alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107604231A CN107604231A (en) | 2018-01-19 |
| CN107604231B true CN107604231B (en) | 2019-04-30 |
Family
ID=61061962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710821976.9A Active CN107604231B (en) | 2017-09-12 | 2017-09-12 | A kind of high pressure resistant high-temperature rigid alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107604231B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108441736A (en) * | 2018-04-26 | 2018-08-24 | 济南大学 | Powdered metallurgical material and inlay blade preparation method |
| CN108642402B (en) * | 2018-06-04 | 2020-11-03 | 湘潭大学 | Aluminum nitride dispersion strengthening powder metallurgy aluminum high-speed steel and preparation method thereof |
| CN111375763B (en) * | 2018-12-27 | 2021-03-16 | 四川大学 | AlN-based surface-layer beta-phase-removed gradient hard alloy cutter material and preparation method thereof |
| CN109652729A (en) * | 2018-12-28 | 2019-04-19 | 河源正信硬质合金有限公司 | A kind of hard alloy high temperature high voltage resistant anvil and preparation method thereof |
| CN111500914A (en) * | 2020-04-26 | 2020-08-07 | 山东沂水机床厂有限公司 | Hard alloy for numerical control machine tool and preparation method thereof |
| CN111360309A (en) * | 2020-04-28 | 2020-07-03 | 山东沂水机床厂有限公司 | Transverse multi-cutter bidirectional planing type planer and using method thereof |
| CN112695238A (en) * | 2020-12-22 | 2021-04-23 | 厦门大学深圳研究院 | Vanadium-titanium composite binder phase hard alloy and preparation method thereof |
| CN115074592A (en) * | 2022-06-28 | 2022-09-20 | 河源正信硬质合金有限公司 | High-temperature-resistant high-toughness hard alloy material for die and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5413514A (en) * | 1977-07-01 | 1979-02-01 | Sumitomo Electric Industries | Coated super hard alloy parts |
| CN104911431A (en) * | 2015-06-26 | 2015-09-16 | 河源正信硬质合金有限公司 | High-toughness ultra-wear-resistant hard alloy and manufacturing method thereof |
| US10336654B2 (en) * | 2015-08-28 | 2019-07-02 | Kennametal Inc. | Cemented carbide with cobalt-molybdenum alloy binder |
| CN106191608B (en) * | 2016-08-23 | 2017-09-05 | 河源正信硬质合金有限公司 | A kind of hard alloy in low cobalt of high temperature resistant, wear resistant corrosion resistant and preparation method thereof |
-
2017
- 2017-09-12 CN CN201710821976.9A patent/CN107604231B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107604231A (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107604231B (en) | A kind of high pressure resistant high-temperature rigid alloy and preparation method thereof | |
| CN109371307A (en) | It is a kind of using high-entropy alloy powder as the preparation method of the WC base cemented carbide of binder | |
| CN101837458B (en) | Iron alloy-based composite hard alloy roller and production method thereof | |
| CN106191608B (en) | A kind of hard alloy in low cobalt of high temperature resistant, wear resistant corrosion resistant and preparation method thereof | |
| CN108823478A (en) | Ultra-fine high-entropy alloy Binder Phase cermet and preparation method thereof | |
| CN110373561B (en) | Method for preparing high-density fine-grain titanium alloy through powder forging | |
| CN108723371A (en) | A kind of high-entropy alloy reinforced aluminum matrix composites and preparation method | |
| CN110846547A (en) | High-entropy alloy combined tungsten carbide hard alloy and preparation method thereof | |
| CN109112378A (en) | A kind of preparation method of new bonding phase cemented carbide material | |
| CN110205536B (en) | Titanium/titanium carbide core-shell structure reinforced aluminum-based composite material and preparation method thereof | |
| CN110923535A (en) | Hard alloy and preparation method and application thereof | |
| CN109868404A (en) | A kind of hard alloy axle sleeve and preparation method thereof | |
| CN111235452A (en) | Ti (C, N) -based hard alloy material and preparation method thereof | |
| CN110791682A (en) | Preparation method of powder metallurgy titanium alloy | |
| CN106002131B (en) | A kind of embedded alloy high-performance shearing dise knife and its processing method | |
| CN112266251A (en) | Preparation method of silicon nitride/titanium carbide ceramic material based on spark plasma sintering | |
| CN107619980B (en) | A kind of ultra-fine grain cobalt-free hard alloy and preparation method thereof | |
| CN109694971B (en) | Powder metallurgy titanium-aluminum-based composite material and preparation method thereof | |
| Xiao et al. | Microstructure and mechanical properties of powder metallurgy Ti-Al-Mo-V-Ag alloy | |
| CN107287461B (en) | A kind of Ultra-fine Grained high performance Ti (C, N)-TiB2- WC-TaC composite cermets cutter and preparation method | |
| CN109913706A (en) | A kind of hot pressing for aluminum silicon carbide composite material method | |
| CN112143925A (en) | Preparation method of high-strength high-plasticity titanium-magnesium composite material | |
| CN108411179B (en) | Multiphase titanium diboride/titanium carbonitride cermet and preparation method thereof | |
| CN107287472B (en) | A kind of viscose staple fibre cutoff tool that the powder metallurgic method mixed with pure powder manufactures | |
| CN109794606A (en) | A kind of titanium alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A high pressure and high temperature resistant cemented carbide and its preparation method Effective date of registration: 20210426 Granted publication date: 20190430 Pledgee: Heyuan Branch of China Construction Bank Co.,Ltd. Pledgor: HEYUAN ZHENGXIN HARDMETAL CARBIDE Co.,Ltd. Registration number: Y2021980003038 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220630 Granted publication date: 20190430 Pledgee: Heyuan Branch of China Construction Bank Co.,Ltd. Pledgor: HEYUAN ZHENGXIN HARDMETAL CARBIDE Co.,Ltd. Registration number: Y2021980003038 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |